an Office of Basic Energy Sciences

Energy Frontier Research Center

Fluid Interface Reactions, Structures and

Transport (FIRST) Center

David J. Wesolowski (Oak Ridge National Lab)

FIRST Center Vision and Goal

To develop quantitative and

predictive models of the unique

nanoscale environment at fluid-solid

interfaces to enable transformative

advances in electrical energy

storage and heterogeneous

catalysis.

RESEARCH PLAN AND DIRECTIONS

Our multidisciplinary team integrates advanced materials synthesis, neutron

and X-ray scattering, various spectroscopies, macroscopic experiments, and

multiscale molecular modeling to provide a predictive capability for controlling

and designing new interfacial systems for 21st century energy needs.

Thrust 1: Fluid-Solid Interface (FSI) Model Development

Peter T. Cummings, Leader

Goal is to develop quantitative and predictive Fluid-Solid Interface (FSI) models

for relevant fluid/substrate combinations (e.g, water, ionic liquids, polar

organics, carbon, oxides) guided by experimental input.

− Integrated Theory, Modeling, Simulation, and Experiments, ITMSE, across

the relevant time and length scales is the guiding concept.

.

2

Ovals are

Experimental

Methods

Rectangles

Are Modeling

Approaches

Thrust 2: Nanotextured and Reactive Substrates

Sheng Dai, Leader

Ion transport in electrolyte, intercalation

into electrodes and Solid-Electrolyte

Interphase (SEI) formation are all poorly-

understood, but limiting phenomena in,

for instance, Li-ion batteries.

In electrochemical capacitors “super-

capacitance” is postulated to result

when electrode nanopores are filled

with „bare‟ ions, free of their electrolyte

solvation shells.

Goal is to understand and control ion transport, charge/discharge processes

and substrate evolution at nanotextured and reactive battery and

supercapacitor electrode/electrolyte interfaces.

3

Thrust 3: Fluid-Mediated Surface Reactions

Steven H. Overbury, Leader

Goal is to understand and control fluid-mediated proton-coupled electron

transfer (PCET) in photocatalytic and electrocatalytic reactions at fluid-solid

interfaces, such as CO2 and O2 reduction in H2O CO2 and other dense fluids.

0.5 V-NHE

COOH*

CO* +H2O*

CO2*

0

1.1

0.6

2.1

2.3

1.9

+H+ + e-

+0.3

+0.9

1.0

+H+ + e-

+2H+ + 2e-

HCOO*

HCOOH*

+H+ + e-

+H+ + e-

0.5 V-NHE

COOH*

CO* +H2O*

CO2*

0

1.1

0.6

2.1

2.3

1.9

+H+ + e-

+0.3

+0.9

1.0

+H+ + e-

+2H+ + 2e-

HCOO*

HCOOH*

+H+ + e-

+H+ + e-

Role of surface anchored

proton donor ligands in

oxygen reduction reaction

rates?

carbon

O=O

Pt

H+

carbon

O=O

Pt

H+O=O

Pt

H+

=O

C−O−

carbon

O=O

Pt

H+

carbon

O=O

Pt

H+O=O

Pt

H+

=O

C−O−

=O

C−O−C−O−

O2 + 4H+ + 4e- 2H2O

CO2 + 2H+ + 2e- HCOOH

PCET at FSI

Energetics of CO2 reduction from

first principles. Functional

groups at

graphene

edges.

H2O + CO2 at Pt on carbon

4

Beamline ID-

6

Beamline ID-33

Advanced Photon Source

sample cell

Sector 6 Sector 33

Fenter’s

Beam

Lines

Argonne National

Laboratory’s Advanced

Photon Source is the

Western Hemisphere’s

Brightest X-ray source,

making it an ideal facility

for probing fluid-solid

Interfaces in situ.

Current (Nanoman, MFP-3D, and Cypher)

ambient/SPM platforms at CNMS. Figures

are courtesy of Veeco and Asylum Research

NanoTransport System for in-situ oxide growth, surface

characterization, and UHV STM and PFM studies.

ORNL’s SNS/HFIR and CNMS provide a wealth of unique capabilities free to users.

SNS

CNMS

Mamontov

Inside

BASIS

spectrometer

Kalinin/Balke labs in CNMS Kolesnikov’s

INS instrument

3-stories high!

ORNL’s National Center for Computational Sciences, a DOE user facility, is home to the

world’s most powerful open-system high performance computing platform. This combined

with CNMS Nanomaterials Theory Institute (Cummings, Director) and our newly-purchased

Institutional Computational Cluster and 700,000 hour NERSC allocation gives FIRST Center

researchers unprecedented access to a wide range of computing facilities.